Pigmenting compositions for textile fabric



' Patented June 5, 1945 PIGMENTING coMrosrrIoNs FOR, 'rax'rmn FABRIC v Paul Louis Meunier,

Wilmington, Deb, assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application November 17, 1942,

Serial 170,465,906

30mins. j (01. 106-123) This invention relates to pigment color pastes for such textile printing and dyeing processes wherein the color is applied to the fabric in the form of pigment Jointly with water-dispersions of heat covertible starches, in other words, starch Y derivatives in which the hydrophilic groups have been blocked by organic radicals to convert the starch, when dried and heated upon the fiber,

into a water-resistant film. itarch derivatives or starch preparations of this type and methods of producing them are described, for instance,

in U. S. Patents Nos. 2,125,901, 2,292,921, and 2,267,277. It is the common property of such starch derivatives or preparations that while being soluble in water to facilitate'their application to textile fabric, they become readily converted into water-insoluble films upon the fiber, if the latter is dried and heated to a temperature between 100 and 150 C.

The art of printing textile fabric with colored printing pastes based on a water-soluble gum,

such as starch or gum-tragacanth, which is subsequently washed out of the fabric, is old and well known. A recent trend in the printing art, however, is to print fabric with printing pastes in which the pigment is dispersed in a heat-convertible starch, in other words, a starch modified to'such an extent that upon drying it yields a water-insoluble film, and which consequently does not wash out but remains on the fabric as a permanent protection for the pigmented design imprinted. A similar process has been developed for pigment dyeing wherein the fabric is impregnated in an aqueous bath containing a pi ment in dispersed form and also a modified starch of the mentioned type, so that upon dryin the fiber a water-insoluble colored film is developed upon the fiber. Commercial examples of such modified starches are Shopal #8, Shopal #10,

. ShopalDR'T, etc. (marketed by Stein, Hall 81 Co.)

which are understood to be derivatives of starch,

produced by blocking the hydrophilic groups of the starch with organic radicals and yielding, upon drying, water-resistant films. (See American Dyestuff Reporter, vol. 32, p. 96, February 15, 1943.) These starch derivatives .are dried on the fabric at temperatures ranging from 170 F. to 210 F.; thus, they envelop the dispersed pigments in water-resistant films which bind the pigments to the cloth.

The advantages of such modified printing or dyeing methods are self-evident. They suffer,

-thalene-sulfoniceacid-formaldehyde proved by however, from the drawback that uniform dispersion of the pastes of this type is diflicult to obtain. Many pigments, especially thos of the phthalocyanine series and many vat dyes, are by their nature dimcult to disperse. Consequently the commercial color pastes of these pigments contain admixed therewith dispersing agents of the higher alcohol-sulfate type (Gardinpls) or of the naphcondensation-product type (U. S. P. 2,213,693). In some of these colors, nevertheless, the pigment particles are flocculated to such an extent that, unless excessive quantities of the dispersing agent are employed, specky prints and considerable loss of strength result. While this condition maybe improduct or by milling the pigment-dispersionstarch-derivative paste in a colloid mill or paint mill, or by high-speed agitation, such practices are expensive and objectionable, since they cause an initial thinning of the printing paste and furthermore increase its-tendency to gel upon standing. In the case of printing, excessive reductions in printing paste viscosity are objectionable because. they invariably result in weaker, duller prints, due to excessive penetration of the fabric. Thickening, on the other hand, renders the printing paste mechanically inapplicable.

Accordingly, this invention has for an object to provide a method for the dispersion of waterinsoluble pigments in binders of starch origin which deposit water-resistant films upon drying. A further object is to accomplish this dispersion without, causing undesirable viscosity variations in the starch derivative vehicle, e. g., initial thinfurther object is to effect and maintain the dispersion of pigments in the starch derivative vehicles by means of a reagent which is universally eflective with a wide variety of pigment and which is not readily p of the system.

Now, according to the present invention, the above and further objects of this invention are accomplished neatly by adding to the commercial pigment in starch derivative using an excess of said condensation affected by variations in the acid and its water-soluble salt for the l the printing pastes.

, Almy Co., and believed to suli'oni'cs, acids (or -in order to study its effect on dispersing agents but preferably prior to its incorporation with said heat-convertible starch type printing paste, a member of the group conslstlng of the lignin-sulfonic acids and watersoluble salts thereof.

The excellent performance of lignin-sulfonic of this invention is both unique and unexpected. For although lignin-sulfonic acid and'its salts are well known as anti-coagulants, other agents which belong in the same classification perform to a much inferior degree or accomplish only some, but not all, the objects of this invention. Thus, I have tested protective agents of the following types:

Triethanolaminelauric acid ester, Methylol urea-protein formaldehyde condensasion product (a commercial dispersing agent), Suli'onated ortho-benzoyl-benzoic acid, Stearamido-methyl-pyridinium-bromide,

and found that in each case their performance was inferior to lignin-sulfonic acid or its trisodium salt as regards the tinctorial strength obtained in the starch derivative vehicle and also as regards the adverse effects of these protective agents on the starch derivative itself; i. e., thinning, gelling, and variations in the "length" of Length" is a test applied in practice by the printer to determine'the printing qualities of the paste.

purpose 4 210 F., to dry the colored starch cotton, cellulose ester, nylon,

The above ingredient aremilled together in a colloid mill, and the composition is then added to 900 parts of a 5% aqueous dispersion of a heat- The pigment color paste and starch derivative are mixed together in an open vessel by stirring slowly. The pigment color disperses uniformly throughout the composition,.'producing astrong coloration in a. few minutes. The printing paste thus prepared is printed on textile fabric, e. g.,

' regenerated cellulose, silk, wool, etc. from an engraved printing roller. The printed fabric is then passed over steam heated cans, at-a temperature of 170 to derivative into a water-insoluble film on the fabric.

In addition to the above superiority, the lig'nin,

soluble salts thereof) when used in this invention are apparently less affected by variations in pH than the other agents listed above. This important advantage has been demonstrated by a series of experiments in which the pH of the color dispersion was purposely varied Y incorporation of such color dispersion with the starch derivative binders above defined. It was each of the agents above, -a printing paste deliberately acidified to a pH 01 about 3.0 gave a print of far less strength and speckled to a much greater degree thanwhen thesame agent was employed at (5 to 7).

fonicacid and its trisodium -salt, tested under same high quality were obtained regardless. of I the pH value of the paste.

Without limiting my invention, the following examples are typical of my preferred process. Parts mentioned are .by weight.

' In these examples where lignin-sulfonic acid is specified, the product known as Hornkem #1 (Horn Research Laboratories, Inc., I.ong Island, New York), which is believed to be a purified ligninesulfonic acid, was used by me. Representing the salt, Daxad #23, produced 'by Dewey &

of lignin-sulfonic'acid was employed.

. Example! A pigment color paste is prepared as follows:

be the trisodium salt found that with 1 its normal pH in the resulting paste In the cases, however, of lignin-sul-l 5 f-m'aterialis Naphthalene sulfonic' acid-formaldehyde ably brighter Prints thu produced arestronger, brighter, smoother and leveler than prints produced from pigment color pastes containing no lignin-sulfonic acid (or salt), i. e., a metal-free phthalo-v cyanine paste containing only a naphthalene sulfonic acid-formaldehyde condensation product as dispersing agent.

Example 2 Metal free phthalocyanine pulp (dry basis)- 20.0 Water 78.7.

N aphthalene sulfonic acid-formaldehyde condensation product 0.3 Ligninsulfonic acid trisodium salt 1.0 Total 100.0

The lignin-sulfonic acid trisodium' salt is added to a mixture of the other ingredients, and the entire composition is milled in a colloid-mill until uniform. The resulting composition is then added to 900 parts of a starch derivative binder paste as in Example 1 and prints'are produced in the manner described in said example. The printing paste possesses advantageous properties similar to those of Example 1 and the resulting prints possess similar advantages in strength, brilliance, smoothness, and levelness over prints produced from the same pigment and binder without the aid oflignin-sulfonic acid (or salt thereof).

Example 3 Parts Copper phthaiocyanine pulp (dry basis) condensation product I, 1.5

" Water g 755 Lignin-sulfonic acid or salt (dry basis) 3.0

Q Total 100.0

f The ligninesulfonic acid (or salt) is added I a mixture of the other ingredients, and the entire composition is milled in a- Follows and Bates l mill 'u'ntil uniform.

; 0 parts 01' this paste arellnoo p rabd with 990 parts of a starch-derivative hinder paste -(5%), for instance the binder reprue'nted by Bhopal #aor Bhopal #10, marketed by Stein. Hall a 00. (These are believed to be derivatives of starch, produced by-starch to such an extent upon drying. water-resistant films.) printing paste is printed on textile dried at to 210 obtained are much leveler.

than prints F. The prints stronger and appreciconvertible starch-derivative binder, e. g., Shopal and the printed obtained with I w pastes prepared from the same color and binder in the normal way, i. e., by using the same dispersing agent without the aid of. lignin-sult'onic acid or its salts. Furthermore, the printing results obtained with, lignin-sulfonic acids or their salts are superior to those produced by using in their stead any of theothe'r protective agents above listed. 1

In a similar manner my invention may be applied to-improve the process and results obtained in pigment-dyeing of fabric by the aid of modified starch binders. The essential difference between such dyeing processes and the printing processes above illustrated is that a less viscous modified starch binder is employed, so that upon dispersion in the aqueous dye bath to' a concentration of, say, between 1 to 6%, the resulting bath .is still sufliciently fluid to be employed as a dyeing bath, as contrasted to a printing paste. The following additional example will illustrate'the pro 1 cedure in this type of dyeing.

Example 4 3.0 parts of lignin-sulfonic acid (or a salt thereof). are milled in a colloid mill with a mixture of 20.0 parts of copper phthalocyanine, 1.5 parts of 1 naphthalene-sulfonic-acid-iormaldehyde condensation product and 75.5 parts of water as in Example 3. The resulting color paste is incorporated into 900 parts of a 5% dispersion of Shopal DRT in water, by slow stirring as in Example 1. Textile ilber, for example,', cotton. regenerated cellulose, cellulose acetate, nylon, silk or wool, is passed through the resulting dye bath and then through squeeze rollers to remove excess liquor. The fiberis then passed over drying drums at a temperature of 170 to 210 F. The dyeing produced in this manner is stronger. brighter and leveler than dyeings obtained from the same color and a similar pigment-dyeing bath but without the aid of lignin-sulfonic acid or a salt thereof.

It will be understoodthat the above examples are merely illustrative and that the details of 45 procedure or compositionmay be varied consider- .ably within the skill of .thoseiengaged in this art. For instance, the proportion of lignin-sulionic acid (or salt) to pigment in-the color paste may vary from 0.025 to 0.25 by weight. The ratio of pigment to modified starch binder in the eventual printing paste or dyeing bath may vary from 0.02 to 0.5 by weight on dry basis.

The incorporation of the lignin-sulfonic acid or its salt'with the pigment may be achieved by milling in a colloid mill, as above specified; or by means of dry milling (milling the dry pigment with the dry protective agent), viscous milling (by means of a Werner and Pfleiderer mixer), or

any of the other known methods of incorporating m are'rnuch more consistent in their operative scope than those other agents described above (tri- 70 ethanolamine-lauric acid ester, etc.). Following are the operative concentrations of'our preferred anti-co'agulants, i. e., lignin-sulfonic acids and their salts, as applied to several pigment nnlnrn mm for printing and for pigment-dyeing. 7B

Operative concentrations o1 llgninsulfonic acid or the trisodium salt (per cent by weight of color composition bcto re incorporating the modified starch binder) Per cent Copper phthalocyanine, paste l to 3 Highly chlorinated copper phthalocyanine, 20%

paste 1 to 3 Benzidine Yellow (3,3-dichlorobcnzidine tettrazotized and coupled to 2 moles of acetoacetanilidc), 20% paste 0. 5 to 2 Metal-free phthalocyanine, 20% paste 1 to 3 Mono-chlorinated lndanthrone. 16.5% pas (Col. Ind. #1113) 2 to 4 N aphthol Red (p-nitro-o-toluidine diazotized and coupled to p-cliloro-anilide of 2,3-liydroxy-napht-hoic acid 0. 5 to 2 Vat Yellow, 001. Ind. #1132, 20% paste O. 5 to 3 Thioindigoid Pink (Prototype #109, 1940 Yearbook, Am. Ass'n Text. Chem. 61 Color.),

14% pastc 0.2 to l. 5 Vat Bed (Prototype #124, ibid), 20% aste 2.0 to 5. 0 Benndine Orange (3'3'-dichloro-benz dine tetrazotized and coup ed to 2 moles of l-phenyl- 3-methyl-5-pyrazolone), 21% paste 0. 5 to 2 forces which cause gelation in a colloidal system such as are obtained with the heat-convertible starch binders.

7 However, regardless of theory, the pigment dispersions with lignin-sulfonic acids (or salts) described above have the following distinct advantages over other types of dispersing agents and dispersions when used with the above-mentioned modified starch binders:

1'. Greater ease of incorporation: Thismeans that mixing with simple agitation, such as a. slow paddle mixer, produces a uniform dispersion of the pigment in the binder. Uniformity oi. the dispersion is shown by the absence of flocculation when examined under the microscope and strong, full and bright prints, free from specks.

2. Smoother prints and dyeings; longer" printing pastes; and more stable printing pastes and pigment-dye baths. For example, the naphthalene-sulfonic acid-formaldehyde condensation products cause the printing pastes to setup or become gelled on standing, while the pastes prepared with the mentioned lignin derivatives either remain unchanged or become gelled to only a comparatively slight degree,

3. Prevention of flocculation of pigment in the dye bath' or printing paste, regardless whether the free lignin-suli'onic "acids are used at pH values as low as 2.0 or whether the neutral salts, e. g., trisodium lignin-sulfonate (pH=about 7.0),

are used. Other agents are very sensitive to pH variation on the acid side (pH 3.0; see above).

a 4. Eflfective range of concentrations of the protective agent is low. (See above table, listing effective concentrations.)

I claim as my invention: 1. A pigmenting composition for textile fabric,

comprising a, water-insoluble organic pigment,

water, a heat-convertible starch derivative, and a capillary-active agent, said heat-convertible starch derivative being a water-insoluble, partially esterifled starch'characterized by the prop erty of taming a water-resistant film upon dryfrom the group consisting of lignin-sulionic acid the other hand. 1

3. A pigmenting composition for textile fabric and its water-soluble salts, the proportion of piganine series, a heat-convertible starch-derivati e 7 being a partially esterifled starch and being adapted to produce a water-resistant film upon heating after application to the textile fiber, and

ment to starch derivative by weight being bea a mixure of capillary-active agents comprising tween 0.02:1 and 0.50:1, and the proportion. of on the one hand a member 01' the group consist-. said capillary-active agent being from 4 to A ing of formaldehyde-naphthalene-sulfonic acid by weight of the dry pigment. condensation product and its water-soluble salts 2. A pigmenting composition as in claim 1, the and on the otherihand a member of the group capil1ary-active agent comprising a mixture of a 10 consisting of lignin-su'lfonic acid'and its water.-

- member oi'the group consisting of formaldehydesoluble salts, the quantity of the second-mennaphthalene-sulfonic-acidcondensation product tioned component of said mixture being from .1 and water-soluble salts thereof on the one hand, to 3 parts by weight for each parts by weight and a member of the group consisting or ligninof said pigment, and the quantity of pigment sulfonic acid and water-soluble Salts thereof on. 15 being between-2 and parts by weight for each parts by weight of said heat-convertible starch-derivative.

comprising water, a pigment of the phthalocy- I PAUL LQU'IS p I CERTIFICATE or CORRECTION, -Patent ms." 2,577,709. June .19L 5.

PAULLOUIS 'I'EEUNIER.

It is-her eby certified that error appears intheprinted specification of the above numbered patent requiring correction as followsrfage 2, secondeolumn, 1ine'69, after the word "by in sert -.-partialiy esterifying-w v and thatthe said Letters Patent should"be read with th iacorrection therein thatfthe same may conform to the reco m fcthe caan-".i; h e Patent Office. Signed and sealed this 18th day of September} A. n. 1915-.

I Leslie Frazer (Seal) First Assistant iiommjissioner'of Patents.

from the group consisting of lignin-sulionic acid the other hand. 1

3. A pigmenting composition for textile fabric and its water-soluble salts, the proportion of pigasvzvoo anine series, a heat-convertible starch-derivati e 7 being a partially esterifled starch and being adapted to produce a water-resistant film upon heating after application to the textile fiber, and

ment to starch derivative by weight being bea a mixure of capillary-active agents comprising tween 0.02:1 and 0.50:1, and the proportion. of on the one hand a member 01' the group consist-. said capillary-active agent being from 4 to A ing of formaldehyde-naphthalene-sulfonic acid by weight of the dry pigment. condensation product and its water-soluble salts 2. A pigmenting composition as in claim 1, the and on the otherihand a member of the group capil1ary-active agent comprising a mixture of a 10 consisting of lignin-su'lfonic acid'and its water.-

- member oi'the group consisting of formaldehydesoluble salts, the quantity of the second-mennaphthalene-sulfonic-acidcondensation product tioned component of said mixture being from .1 and water-soluble salts thereof on the one hand, to 3 parts by weight for each parts by weight and a member of the group consisting or ligninof said pigment, and the quantity of pigment sulfonic acid and water-soluble Salts thereof on. 15 being between-2 and parts by weight for each parts by weight of said heat-convertible starch-derivative.

comprising water, a pigment of the phthalocy- I PAUL LQU'IS p I CERTIFICATE or coRREc IoN -Patent.pb;-2,577,709. June ,.19h5.

-PAUL Louis MEUNIER.

It is-her eby certified that error appears intheprinted specification of the above numbered patent requiring correction as followsrfage 2, secondeolumn, 1ine'69, after the word "by in sert -.-partialiy esterifying-w v and thatthe said Letters Patent should"be read with th iacorrection therein thatfthe same may conform to the reco m fcthe caan-".i; h e Patent Office. Signed and sealed this 18th day of September, A. n. 19h5;

I Leslie Frazer (Seal) First Assistant iiommjissioner'of Patents. 

